Ambient ozone (O3) in three Class I wilderness areas in the northeastern USA: measurements with Ogawa passive samplers

Ambient ozone (O(3)) was measured in two Class I wilderness areas, one within the White Mountain National Forest in north central New Hampshire (NH) and one within the Green Mountain National Forest in southwestern Vermont (VT), for six weeks between 5 July and 16 August 1994, using Ogawa passive nitrite-coated filter samplers and a one week exposure period each time. Results for 7-day mean ambient O(3) concentrations from the passive samplers were compared to results from a co-located continuous ultraviolet photometric O(3) analyzer both in NH and VT. Although the size of the data set was small, agreement through simple linear regression between mean 7-day O(3) concentrations determined by the continuous monitors, and those obtained from the passive samplers was generally very good (adjusted R(2) = 0.759; p = 0.0003). Overall, excluding the one outlier value, any observed differences in the results obtained by the two methods when comparing co-located passive samplers to the continuous monitor within a given study location, appeared to be solely due to experimental error.     

A multi-variate statistical model integrating passive sampler and meteorology data to predict the frequency distributions of hourly ambient ozone (O3) concentrations

A multi-variate, non-linear statistical model is described to simulate passive O3 sampler data to mimic the hourly frequency distributions of continuous measurements using climatologic O3 indicators and passive sampler measurements. The main meteorological parameters identified by the model were, air temperature, relative humidity, solar radiation and wind speed, although other parameters were also considered. Together, air temperature, relative humidity and passive sampler data by themselves could explain 62.5-67.5% (R(2)) of the corresponding variability of the continuously measured O3 data. The final correlation coefficients (r) between the predicted hourly O3 concentrations from the passive sampler data and the true, continuous measurements were 0.819-0.854, with an accuracy of 92-94% for the predictive capability. With the addition of soil moisture data, the model can lead to the first order approximation of atmospheric O3 flux and plant stomatal uptake. Additionally, if such data are coupled to multi-point plant response measurements, meaningful cause-effect relationships can be derived in the future.     

Outdoor/Indoor/Personal ozone exposures of children in Nashville, Tennessee

An ozone (O3) exposure study was conducted in Nashville, TN, using passive O3 samplers to measure six weekly outdoor, indoor, and personal O3 exposure estimates for a group of 10- to 12-yr-old elementary school children. Thirty-six children from two Nashville area communities (Inglewood and Hendersonville) participated in the O3 sampling program, and 99 children provided additional time-activity information by telephone interview. By design, this study coincided with the 1994 Nashville/Middle Tennessee Ozone Study conducted by the Southern Oxidants Study, which provided enhanced continuous ambient O3 monitoring across the Nashville area. Passive sampling estimated weekly average outdoor O3 concentrations from 0.011 to 0.O30 ppm in the urban Inglewood community and from 0.015 to 0.042 ppm in suburban Hendersonville. The maximum 1- and 8-hr ambient concentrations encountered at the Hendersonville continuous monitor exceeded the levels of the 1- and 8-hr metrics for the O3 National Ambient Air Quality Standard. Weekly average personal O3 exposures ranged from 0.0013 to 0.0064 ppm (7-31% of outdoor levels). Personal O3 exposures reflected the proportional amount of time spent in indoor and outdoor environments. Air-conditioned homes displayed very low indoor O3 concentrations, and homes using open windows and fans for ventilation displayed much higher concentrations.     

Passive sampling of ambient, gaseous air pollutants: an assessment from an ecological perspective

During some past two decades there has been a growing interest among air pollution-vegetation effects-scientists to use passive sampling systems for quantifying ambient, gaseous air pollutant concentrations, particularly in remote and wilderness areas. On the positive side, excluding the laboratory analysis costs, passive samplers are inexpensive, easy to use and do not require electricity to operate. Therefore, they are very attractive for use in regional-scale air quality assessments. Passive samplers allow the quantification of cumulative air pollutant exposures, as total or average pollutant concentrations over a sampling duration. Such systems function either by chemical absorption or by physical adsorption of the gaseous pollutant of interest onto the sampling medium. Selection of a passive sampler must be based on its known or tested characteristics of specificity and linearity of response to the chemical constituent being collected. In addition, the effects of wind velocity, radiation, temperature and relative humidity must be addressed in the context of absorbent/adsorbent performance and sampling rate. Because of all these considerations, passive samplers may provide under- or overestimations of the cumulative exposures, compared to the corresponding data from co-located continuous monitors or active samplers, although such statistical variance can be minimized by taking necessary precautions. On the negative side, cumulative exposures cannot identify short-term (相似文献   

Estimates of ozone AOT40 from passive sampling in forest sites in South-Western Europe

Weekly-fortnightly ozone (O3) concentrations measured by passive sampling at 81 forest monitoring plots in France, Italy, Spain and Switzerland over the period 2000-2002 were used to estimate the cumulative exposure index AOT40. The estimation method is based on a deterministic model which describes the O3 daily profile as a function of relative altitude (the difference between the altitude of the site and the lowest altitude within a 5 km radius) and the time of the day. Estimated AOT40 values (AOT40(e)) were evaluated against co-located automatic measurement stations and with 14 independent automatic stations located throughout Italy whose weekly mean O3 values were used to simulate passive samplers. AOT40 can be predicted by modelling passive sampling data (R2: 0.90; P<0.0001, SE of estimates: 3271 ppb h), although considerable deviations can occur for individual sites. Estimated AOT40 shows a distinct, significant latitudinal and altitudinal gradient. Taking the 3-year average as a whole, exceedance of critical level of 5000 ppb h occurs at 77-100% of the monitored sites, respectively.     

PLATIN (plant-atmosphere interaction) II: Co-occurrence of high ambient ozone concentrations and factors limiting plant absorbed dose

There is an ongoing debate as to which components of the ambient ozone (O3) exposure dynamics best explain adverse crop yield responses. A key issue is regarding the importance of peak versus mid-range hourly ambient O3 concentrations. While in this paper the importance of peak atmospheric O3 concentrations is not discounted, if they occur at a time when plants are conducive for uptake, the corresponding importance of more frequently occurring mid-range O3 concentrations is described. The probability of co-occurrence of high O3 concentrations and O3 uptake limiting factors is provided using coherent data sets of O3 concentration, air temperature, air humidity, mean horizontal wind velocity and global radiation measured at representative US and German air quality monitoring sites. Using the PLant-ATmosphere INteraction (PLATIN) model, the significance of the aforementioned meteorological parameters on ozone uptake is examined. In addition, the limitations of describing the O3 exposure for plants under ambient, chamberless conditions by SUM06, AOT40 or W126 exposure indices are discussed.     

Application of ground-based Lidar for studies of the dynamics of ozone in a mountainous basin

A ground-based Differential Absorption Lidar was employed to study the dynamics of atmospheric O3 within the planetary boundary layer of a basin in the 'Fichtelgebirge' mountains, NE Bavaria. In particular, the night-time dynamics of O3 linked to the ground were investigated. The Lidar system measured vertical profiles of O3 up to 1 km above ground. For detailed analysis of the night-time dynamics of ozone, supplementary data from three ground-based stations (measuring mixing ratios of O3 and NO(x), as well as meteorological parameters) are essential. The Lidar results could be evaluated with these data from various altitudes above the basin floor. For the station with the largest (vertical) distance to the ground-based Lidar, the agreement was very good at all times. The Lidar method proved to be useful for examining the spatial distribution of O3. The observed night-time decrease of O3 at the bottom of the basin was due to deposition and to advection of air masses containing less O3 from the mountain slopes.     

Impact of ozone on Mediterranean forests: a review

Ozone impact on Mediterranean forests remains largely under-investigated, despite strong photochemical activity and harmful effects on crops. As representative of O3 impacts on Mediterranean vegetation, this paper reviews the current knowledge about O3 and forests in Italy. The intermediate position between Africa and European mid-latitudes creates a complex patchwork of climate and vegetation. Available data from air quality monitoring stations and passive samplers suggest O3 levels regularly exceed the critical level (CL) for forests. In contrast, relationships between O3 exposure and effects (crown transparency, radial growth and foliar visible symptoms) often fail. Despite limitations in the study design or underestimation of the CL can also affect this discrepancy, the effects of site factors and plant ecology suggest Mediterranean forest vegetation is adapted to face oxidative stress, including O3. Implications for risk assessment (flux-based CL, level III, non-stomatal deposition) are discussed.     

Performance evaluation of a tailor-made passive sampler for monitoring of tropospheric ozone

Introduction

This study presents the performance evaluation of a tailor-made passive sampler developed for the monitoring of tropospheric ozone.

Methods

The performance of the passive sampler was tested in the field conditions in terms of accuracy, precision, blank values, detection limit, effects of some parameters such as sampling site characteristics and sampling period on the field blanks, self-consistency, experimental and theoretical uptake rates, shelf life and comparison with commercial passive samplers.

Results

There was an agreement (R ²?=?0.84) between the responses of passive sampler and the continuous automatic analyser. The accuracy of the sampler, expressed as percent relative error, was obtained lower than 15%. Method precision in terms of coefficient of variance for three simultaneously applied passive samplers was 12%. Sampler detection limit was 2.42???g?m^?3 for an exposure period of 1?week, and the sampler can be stored safely for a period of up to 8?weeks before exposure. Satisfactory self-consistency results showed that extended periods gave the same integrated response as a series of short-term samplers run side by side. The uptake rate of ozone was found to be 10.21?mL?min^?1 in a very good agreement with the theoretical uptake rate (10.32?mL?min^?1). The results of the comparison study conducted against a commercially available diffusion tube (Gradko diffusion tube) showed a good linear relationship (R ²?=?0.93) between two passive samplers.

Conclusions

The sampler seems suitable to be used in large-scale measurements of ozone where no data are available or the number of existing automated monitors is not sufficient.     

Filtration of Radioactive Aerosols By Glass Fibers

Abstract

An ozone (O₃) exposure assessment study was conducted in Toronto, Ontario, Canada during the winter and summer of 1992. A new passive O₃ sampler developed by Harvard was used to measure indoor, outdoor, and personal O₃ concentrations. Measurements were taken weekly and daily during the winter and summer, respectively. Indoor samples were collected at a total of 50 homes and workplaces of study participants. Outdoor O₃ concentrations were measured both at home sites using the passive sampler and at 20 ambient monitoring sites with continuous monitors. Personal O₃ measurements were collected from 123 participants, who also completed detailed time-activity diaries. A total of 2,274 O₃ samples were collected. In addition, weekly air exchange rates of homes were measured.

This study demonstrates the performance of our O₃ sampler for exposure assessment. The data obtained are further used to examine the relationships between personal, indoor (home and workplace), and outdoor O₃ concentrations, and to investigate outdoor and indoor spatial variations in O₃ concentrations. Based on home outdoor and indoor, workplace, and ambient O₃ concentrations measured at the Ontario Ministry of the Environment (MOE) sites, the traditional microenvironmental model predicts 72% of the variability in measured personal exposures. An alternative personal O₃ exposure model based on outdoor measurements and time-activity information is able to predict the mean personal exposures in a large population, with the highest R² value of 0.41.     

Detecting ozone and demonstrating its phytotoxicity in forested areas of Poland: a pilot study

Ambient concentrations of ozone (O(3)) were measured and O(3) phytotoxicity to tobacco (Nicotiana tabacum L.) was demonstrated in several forest locations in Poland during a pilot study from July-October, 1991. At southern and central locations in Poland, the 24-hour average O(3) concentrations measured with a UV absorption photometer were in the range of 32-55 ppb, and the corresponding 1-hour maxima in the range of 39-83 ppb. At these locations longer period (four to fifteen days) average concentrations were determined using O(3) passive samplers (DGA, Inc.) and were reaching 60 ppb, while at Bialowieza in eastern Poland O(3) concentrations averaged less than 40 ppb. In Szarow, near the Niepolomice Forest in southern Poland, 1-hour O(3) maxima estimated from the data obtained using passive samplers were about 105 ppb in early September. At several locations in southern and central Poland, extensive O(3) injury was determined on O(3)-sensitive Bel W-3 tobacco plants; such injury did not occur in the Bialowieza Forest of eastern Poland. The results of this pilot study indicate that O(3) is present at phytotoxic levels in southern and central Poland.     

Assessment by laboratory simulation of approaches to amelioration of peat acidification

This study was conducted to determine whether acidic cloudwater and ozone (O3) influence the growth of red spruce (Picea rubens L.) seedlings growing at a high elevation site in the southern Appalachian Mountains. A field exclusion chamber study was established at Whitetop Mountain, VA (elevation 1689 m) which included the following treatments: (1) clouds and O3 excluded (COE); (2) exposure to ambient O3 with clouds excluded (CE); (3) exposure to clouds and O3 (CC); and (4) ambient air plots (AA) that served as a control to evaluate possible chamber effects. After 2 years, seedlings exposed to ambient levels of O3 and cloudwater (AA and CC) did not differ in biomass accumulation, diameter growth, or epicuticular wax amounts from seedlings grown in chambers where pollution levels were reduced (CE and COE). Treatments receiving cloudwater (AA and CC) had statistically lower current-year needle concentrations of Ca and Mg, indicating that the cloudwater exposure dynamics occurring at this site elicited reductions in needle Ca and Mg. Ozone had negligible impact on all of the seedling parameters measured.     

Ambient ozone (O3) and adverse crop response: a unified view of cause and effect

This paper presents a cohesive view of the dynamics of ambient O(3) exposure and adverse crop response relationships, coupling the properties of photochemical O(3) production, flux of O(3) from the atmosphere into crop canopies and the crop response per se. The results from two independent approaches ((a) statistical and (b) micrometeorological) were analyzed for understanding cause-effect relationships of the foliar injury responses of tobacco cv Bel-W3 to the exposure dynamics of ambient O(3) concentrations. Similarly, other results from two independent approaches were analyzed in: (1) establishing a micrometeorological relationship between hourly ambient O(3) concentrations and their vertical flux from the air into a natural grassland canopy; and (2) establishing a statistical relationship between hourly ambient O(3) concentrations in long-term, chronic exposures and crop yield reductions. Independent of the approach used, atmospheric conditions appeared to be most conducive and the crop response appeared to be best explained statistically by the cumulative frequency of hourly ambient O(3) concentrations between 50 ppb and 90 ppb (100 and 180 microg m(-3)). In general, this concentration range represents intermediate or moderately enhanced hourly O(3) values in a polluted environment. Further, the diurnal occurrence of this concentration range (often approximately between 0900 and 1600 h in a polluted, agricultural environment) coincided with the optimal CO(2) flux from the atmosphere into the crop canopy, thus high uptake. The frequency of occurrence of hourly O(3) concentrations > 90 ppb (180 microg m(-3)) appeared to be of little importance and such concentrations in general appeared to occur during atmospheric conditions which did not facilitate optimal vertical flux into the crop canopy, thus low uptake. Alternatively, when > 90 ppb (180 microg m(-3)) O(3) concentrations occurred during the 0900-1600 h window, their frequency of occurrence was low in comparison to the 50-90 ppb (100-180 microg m(-3)) range. Based on the overall results, we conclude that if the cumulative frequency of hourly ambient O(3) concentrations between 50-62 ppb (100-124 microg m(-3)) occurred during 53% of the growing season and the corresponding cumulative frequency of hourly O(3) concentrations between 50-74 ppb (100-148 microg m(-3)) occurred during 71% of the growing season, then yield reductions in sensitive crops could be expected, if other factors supporting growth, such as adequate soil moisture are not limiting.     

A 13-week comparison of passive and continuous ozone monitors at forested sites in north-central Pennsylvania

Ogawa passive O3 samplers were used in a 13-week study (June 1-September 1, 1999) involving 11 forested and mountaintop sites in north-central Pennsylvania. Four of the sites were collocated with TECO model 49 O3 analyzers. A significant correlation (p < 0.0001) was found for 24-hr average weekly O3 concentrations between the two methodologies at the four sites with collocated monitors. As expected, there were positive relationships between increasing elevation of the sites and increasing O3 concentrations. No O3 exposure patterns were found on a west-to-east or south-to-north basis; however, the area known for lower O3 exposures within a smaller subsection of the study area showed consistently lower O3 exposures. Preliminary results regarding relationships of symptom responses within O3-sensitive bioindicators are also presented with black cherry (Prunus serotina, Ehrh.) and common milkweed (Asclepias syriaca, L.) showing clear evidence of increasing injury with increasing O3 exposures. Due to the extremely dry conditions encountered in north-central Pennsylvania during the 1999 growing season, O3-induced symptoms were sporadic and quite delayed until late-season rains during the latter portion of the observation period.     

Simulation of stomatal conductance for Aleppo pine to estimate its ozone uptake

The data from a previous experiment carried out in open-top chambers to assess the effects of ozone (O3) exposure on growth and physiology of Aleppo pine (Pinus halepensis Mill.) were re-assessed to test the performance of the EMEP O3 stomatal conductance model used to estimate tree O3 uptake at a European scale. Aleppo pine seedlings were exposed during three consecutive years to three different O3 treatments: charcoal filtered air, non-filtered air and non-filtered air supplemented with 40 nl l(-1). The results of the model using the default parameterisation already published for Mediterranean conifers showed a poor performance when compared to measured data. Therefore, modifications of g(max), f(min), and new f(VPD), f(temp) and f(phen) functions were developed according to the observed data. This re-parameterisation resulted in a significant improvement of the performance of the model when compared to its original version.     

Ozone and the clean troposphere: ecological implications

In recent years numerous investigations have examined the relationships between chronic ozone (O(3)) exposure and plant responses using statistical or empirical cause-effect models. One of the critically important decisions underlying these studies has been the choice of the control or reference O(3) exposure to which all other treatments are compared. The issue of the control or reference O(3) exposure is a complex one. Does a single ambient control or reference O(3) exposure exist? The approach taken in this paper is to examine the O(3) concentrations in the 'clean troposphere.' One must ask what a clean troposphere is and whether there are any geographic locations in the world today that are totally free of human influences. Data on photochemical oxidants from Fortress Mountain, Alberta, Canada, are examined. A comparison of these data with air quality data from other locations in North America is used to examine the design of vegetation response studies. The need for integrated research design, execution, and evaluation is stressed.     

Investigation of the effects of using single-wall carbon nanotubes (SWCNTs) in ozone measurement with passive samplers

Passive samplers are used in air quality monitoring for many years to compete in terms of being economical with continuous measurement systems. In this study, different amounts of single-wall carbon nanotubes (SWCNTs) were added in the impregnation solution of the filters of passive samplers and the effect on the absorption of ozone studied. The results of the measurement of ozone with varying amounts of SWCNTs added to the impregnation solution of the filters of the passive samplers were compared with the results of the continuous ozone measurement system (CS). Measurements were performed for 7 days and 14 days at two different exposure times. The increase of the amount of SWCNTs on the filters of the passive samplers, however, did not have an effect on the measurement of ozone. The measurement results of the passive samplers of the 14-day exposure periods, alternating with the 7-day exposure periods, were lower considerably than the results of the 7-day exposure.

Implications: The accuracy and the use of passive samplers in SWCNTs are expected to provide high measurement results. Observing the effect of the change in the amount of diffusion of pollutants held in the SWCNT is also one of the expected implications.     

Ozone exposure, defoliation of beech (Fagus sylvatica L.) and visible foliar symptoms on native plants in selected plots of South-Western Europe

The relationships between crown defoliation of beech, visible foliar symptoms on native vegetation and ozone exposure were investigated on permanent monitoring sites in South-Western Europe in the years 2000-2002. Relationships between defoliation of beech and O3 (seasonal mean, 2-week maximum, AOT40) were investigated by means of multiple regression models (11 plots, 1-3 years of data each) and a model based on temporal autocorrelation of defoliation data (14 plots, 1-3 years of data each). Different multiple regression techniques were used. The four models generated (R2=0.71-0.85, explained variance in cross-validation 61-78%) identified several significant predictors of defoliation, with AOT40 (p=0.008) and foliar content of phosphorous (p=0.0002-0.0004) being common to all models. The autocorrelation model (R2=0.55; p<0.0001) was used to calculate expected defoliation on the basis of the previous year's defoliation, and model predictions were used as an estimate of expected defoliation under constant site and environmental condition. Residuals (predicted-measured) plotted against current AOT40 shows that a possible effect of ozone occurs only at very high AOT40 (>35,000 ppbh). O3-like visible foliar symptoms were recorded on 65 species at 47% of the common monitoring sites in 2001 and 38% in 2002. No relationship was found between O3 exposure, frequency of symptomatic sites and frequency of species with symptoms (R2=0.11; p>0.05). A number of questions related to the ecological and methodological basis of the survey were identified. Inherent sampling and non-sampling errors and multicollinearity of the data suggest great caution when examining results obtained from mensurational, correlative studies.     

A statistical approach to estimate O3 uptake of ponderosa pine in a mediterranean climate

In highly polluted sites, stomatal behavior is sluggish with respect to light, vapor pressure deficit, and internal CO2 concentration (Ci) and poorly described by existing models. Statistical models were developed to estimate stomatal conductance (gs) of 40-year-old ponderosa pine at three sites differing in pollutant exposure for the purpose of calculating O3 uptake. Gs was estimated using julian day, hour of day, pre-dawn xylem potential and photosynthetic photon flux density (PPFD). The median difference between estimated and observed field gs did not exceed 10 mmol H2O m(-2) s(-1), and estimated gs within 95% confidence intervals. 03 uptake was calculated from hourly estimated gs, hourly O3 concentration, and a constant to correct for the difference in diffusivity between water vapor and 03. The simulation model TREGRO was also used to calculate the cumulative 03 uptake at all three sites. 03 uptake estimated by the statistical model was higher than that simulated by TREGRO because gas exchange rates were proportionally higher. O3 exposure and uptake were significantly correlated (r2>0.92), because O3 exposure and gs were highly correlated in both statistical and simulation models.